Dehydrogenation of organic chemical hydrides has been improved by reconstructing the catalyst in the form of hierarchical porous structure nanocatalyst, in which the economical Ni was adopted as catalytic component and nano Al2O3-TiO2 hybrid composite as support. The Al2O3-TiO2 composite was prepared by spontaneous self-assembly of nano Al2O3 and TiO2 aggregates by hydrolysis of tetra-n-butyl-titanate under continuous agitation. The multi-scaled distribution of Al2O3-TiO2 aggregates with hierarchy could be observed in dynamic light scattering spectrometer. The aggregates are comprised of nano-sized gamma-Al2O3 and anatase TiO2 crystallites with sizes of about 5 and 7 nm, respectively. The surface modulation by TiO2 could be verified in FTIR Spectra. The migration of Ti species and crystallite growth were hindered by the Al2O3 skeleton and the hierarchical porous structure was sustained during the thermal related process. The multi-scaled distributed pores were confirmed by both TEM analysis and N-2 adsorption results. The results of dehydrogenation experiments showed that the hierarchical porous structure nano Nil Al2O3-TiO2 exhibited superior catalytic performance to Ni/Al2O3 with the optimum conversion of 99.9% at 400 degrees C, while the catalyst of Ni/Al2O3 exhibited only 16.5% under the same condition. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.